FIELD OF THE INVENTION
[0001] The present invention relates to a laser ray transmitting colored polyolefin resin
composition containing an anthraquinone salt forming dye and a method of laser welding
using the laser ray transmitting colored polyolefin resin composition.
BACKGROUND ART
[0002] Laser welding of synthetic resin materials can, for example, be conducted as described
below. As shown in Figure 1, one part incorporating a laser ray transmitting material
and another part incorporating a laser ray absorbing material are brought into contact
with each other. When irradiating laser ray from the laser ray transmitting material
side to the laser ray absorbing material, the laser ray that has transmitted the laser
ray transmitting material is absorbed in the laser ray absorbing material and generates
heat. By this heat, the laser ray absorbing material is molten around the portion
that has absorbed the laser ray, and the laser ray transmitting material is also molten,
the resins of the two parts fuse together, and upon cooling sufficient welding strength
is obtained and the laser ray transmitting material and the laser ray absorbing material
are joined firmly. Features of laser welding include the capability of welding without
bringing the laser ray generation portion in contact with the portion to be welded,
the minimal thermal effect on the surrounding portion because the heating is localized,
freedom from the problem of mechanical vibration, the capability of welding of fine
portions and structures, high reproducibility, maintenance of high air-tightness,
high welding strength, inconspicuous welded portion, and no generation of dust etc.
[0003] Traditionally, resin parts have been joined together by clamping with clamping parts
(bolts, screws, clips, etc.), adhesion using adhesives, vibration welding, ultrasonic
welding, etc. According to laser welding, labor saving, productivity improvements,
production cost reductions, etc. can be achieved because secure welding is achieved
by simple operation to provide strength equivalent to or more than the levels expected
by conventional method and in addition vibration and heat have minimal effects. With
these features, laser welding is suitable for the joining of functional components,
electronic components, etc., for which the avoidance of the influence of vibration
or heat is desired in, for example, automobile industry, electric/electronic industry
and other fields, and is applicable to the joining of resin parts of complex shapes.
[0004] As a technology concerning laser welding,
Japanese Patent Laid-Open No. HEI-11-170371 describes a method of laser welding comprising a process wherein laser ray is irradiated
so that it focuses on a portion where an opaque part comprising a laser ray absorbing
thermoplastic synthetic resin and a colorless transparent part comprising a laser
ray transmitting thermoplastic synthetic resin are in contact with each other. In
this case, however, when viewed from the colorless transparent part side, the welded
portion differs from the non-welded portion in color and smoothness, posing a problem
of poor appearance.
[0005] Additionally,
WO02/36329 describes laser welding of a polyolefin resin using an anthraquinone dye and a perinone
dye as colorants. However, if a common neutral dye is used to color a polyolefin resin,
the dye is unlikely to fix due to the weak binding of polyolefin resins to dyes and
in addition because the neutral dye used is very highly soluble in resins, posing
a problem of the bleeding phenomenon, in which the dye migrates elsewhere in the event
of contact with another polyolefin resin. This has been a critical problem not only
in the use of laser welding, but also in general situations of coloring polyolefin
resins.
[0006] The present invention has been developed in view of the aforementioned problems in
the prior art, and is intended to provide a laser ray transmitting colored polyolefin
resin composition that is highly transmittable for laser ray wavelength band (wavelengths
from 800 nm to 1200 nm, e.g., 808, 820, 840, 940, and 1064 nm), that undergoes no
color fading of the colored polyolefin resin part in the heat treatment process prior
to laser welding of the resin part, that permits laser welding with substantially
no sublimation of dye, and that possesses sufficient anti-bleeding quality, and a
method of laser welding using the same laser ray transmitting colored polyolefin resin
composition.
DISCLOSURE OF THE INVENTION
[0007] The laser, ray transmitting colored polyolefin resin composition of the present invention
contains an anthraquinone salt forming dye (i.e., a salt forming dye composed of an
anionic component which is obtainable from an anthraquinone acid dye and an organic
ammonium component) represented by Formula (1) below:
in Formula (1),
each of A and B independently represents -NH- or -O-,
each of R1 to R3 independently represents hydrogen, an amino group, a hydroxy group or a halogen,
each of R4 to R13 independently represents hydrogen, an alkyl group, a nitro group or a sulfonic group,
Kin+ represents an organic ammonium ion,
m represents 1 or 2, and
n represents I or 2;
the sulfonic group is -SO3 or SO3M, the number of -SO3 being m, M representing hydrogen or an alkali metal, and each of M may be identical
or not provided that the number of SO3M is 2 or more.
[0008] An anthraquinone salt forming dye represented by Formula (1) above fixes stably in
polyolefin resins, in which dyes are unlikely to fix due to weak binding to dyes,
and is well compatible with resins. Therefore, by coloring with this anthraquinone
salt forming dye, it is possible to obtain a laser ray transmitting polyolefin resin
part that is stable to heat, that is unsusceptible to environment, and that possesses
excellent laser transmission.
[0009] A big feature of the above-described anthraquinone salt forming dye resides in that
two of the following structure are present in the anthraquinone structure.
[0010] It is also important that the number of sulfonic groups in the anthraquinone salt
forming dye should be adjusted.
[0011] The laser ray transmitting colored polyolefin resin composition of the present invention
well transmits ray in the wavelength range from about 800 nm by semiconductor laser
to about 1100 nm by YAG laser, i.e. laser ray, exhibits high fastness such as to heat
and light, has a good anti-migration property, chemical resistance, etc., and exhibits
a brilliant color. The colored resin part with this laser ray transmitting colored
polyolefin resin composition permits laser welding without fading of the color of
the resin part in the heat treatment process prior to laser welding, with substantially
no dye sublimation. The laser ray transmitting colored polyolefin resin composition
of the present invention colored using a master batch is more uniformly colored, does
not exhibit light scattering due to the colorant, and exhibits good laser transmission.
[0012] Meantime, the method of laser welding of the present invention comprises welding
a contact portion of a laser ray transmitting material comprising any of the aforementioned
laser ray transmitting colored polyolefin resins and a laser ray absorbing material
by irradiating laser ray so that the laser ray transmitting material transmits the
laser ray and the laser ray is absorbed in the laser ray absorbing material with the
laser ray transmitting material and the laser ray absorbing material in contact with
each other.
[0013] According to the method of laser welding of the present invention, a portion of contact
of a laser ray transmitting material and a laser ray absorbing material can be welded
by irradiating laser ray so that the laser ray transmitting material transmits the
laser ray and the laser ray is absorbed in the laser ray absorbing material with the
laser ray transmitting material and the laser ray absorbing material in contact with
each other. The laser ray transmitting material in this method of laser welding permits
laser welding without fading of the color of the resin part in the heat treatment
process prior to laser welding, with substantially no dye sublimation.
BRIEF DESCRIPTION OF DRAWINGS
[0014]
Figure 1 is a lateral view of the laser welding test.
Figure 2 is an oblique view of the laser welding test.
MODE FOR EMBODYING THE INVENTION
[0015] The laser ray transmitting colored polyolefin resin composition of the present invention
contains at least an anthraquinone salt forming dye represented by Formula (1) above.
Because this anthraquinone salt forming dye has a large molecular weight and is highly
bindable to polyolefin resins, particularly polypropylene resins, it acts effectively
on heat resistance and anti-sublimation quality in the laser ray transmitting colored
polyolefin resin composition of the present invention.
[0016] The polyolefin resin used in the present invention is not subject to limitation.
[0017] As examples thereof, there may be mentioned homopolymers of α-olefins such as ethylene,
propylene, butene-1, 3-methylbutene-1, 4-methylpentene-1 and octene-1 or copolymers
thereof, or copolymers (as copolymers, there may be mentioned block copolymers, random
copolymers, and graft copolymers) of these and other copolymerizable unsaturated monomers.
[0018] Specifically, there may be mentioned polyethylene resins such as high-density polyethylene,
intermediate-density polyethylene, low-density polyethylene, linear low-density polyethylene,
ethylene-vinyl acetate copolymer and ethylene-ethyl acrylate copolymer; polypropylene
resins such as propylene homopolymers, propylene-ethylene block copolymers or random
copolymers and propylene-ethylene-butene-1 copolymers; polybutene-1, poly-4-methylpentene-1,
etc.
[0019] These polyolefin resins may be used singly or in combination of two or more species.
As other examples of polyolefin resins in the present invention, there may be mentioned
polyolefin elastomers such as polypropylene resin elastomers, various thermoplastic
elastomers (including various, rubbers) containing the above-described resins as main
component, polyolefin resins containing synthetic waxes or natural waxes, and the
like.
[0020] In the present invention, it is preferable that, of these, a polypropylene resin
and/or a polyethylene resin be used. A polypropylene resin is particularly preferred.
This polypropylene resin is not subject to limitation and can be used over a broad
range of molecular weight.
[0021] As a polyolefin resin, there may be used an acid-modified polyolefin modified with
an unsaturated carboxylic acid or a derivative thereof, foaming polypropylene containing
a foaming agent added to the resin without affecting the desired effect, and the like.
[0022] As propylene copolymers like as described above, those containing propylene at 75%
by weight or more, particularly at 90% by weight or more, are preferred because they
retain the crystallinity, rigidity, chemical resistance, etc. that characterize polypropylene
resins.
[0023] As specific examples of the aforementioned copolymerizable monomer, there may be
mentioned one species or two or more species of a -olefins having 2 or 4 to 12 carbon
atoms, such as ethylene, 1-butene, isobutene, pentene-1, 3-methyl-butene-1, hexene-1,
4-methyl-pentene-1, 3,4-dimethyl-butene-1, heptene-1, 3-methyl-hexene-1, octene-1,
and decene-1; cycloolefins such as cyclopentene, norbornane, and 1,4,5,8-dimethano-1,2,3,4,4a,8,8a-6-octahydronaphthalene;
dienes such as 5-methylene-2-norbornane, 5-ethylidene-2-norbornane, 1,4-hexadiene,
methyl-1,4-hexadiene, and 7-methyl-1,6-octadiene; vinyl monomers such as vinyl chloride,
vinylidene chloride, acrylonitrile, vinyl acetate, acrylic acid, methacrylic acid,
butyl acrylate, methyl methacrylate, and maleic anhydride; and the like.
[0024] An anthraquinone salt forming dye in the present invention can be obtained by a salt-forming
reaction of an anion from an anthraquinone acid dye and an organic ammonium ion (e.g.,
cations from primary amine, secondary amine, tertiary amine, guanidines, or rosin
amines, etc.). This salt-forming reaction may employ a commonly known ionic reaction.
For example, an acid dye component having two sulfonic groups is dispersed in water,
an organic amine component in a ratio of 1.5 to 2.3 mols per mol of the dye is dissolved
in aqueous hydrochloric acid; this solution is added drop by drop to the dispersion
liquid, and the reaction is carried out with stirring for several hours. By filtering
this reaction mixture, washing the cake filtered out with water, and drying it, an
anthraquinone salt forming dye of the present invention can be obtained.
[0025] With respect to Formula (1) above, which represents an anthraquinone salt forming
dye in the present invention, A, B and R
1 to R
13 represent the following groups or atoms, respectively.
[0026] Each of A and B independently represents -NH- or -O-.
[0027] Each of R
1 to R
3 independently represents hydrogen, an amino group, a hydroxy group or a halogen (e.g.,
Cl, Br).
[0028] Each of R
4 to R
13 independently represents hydrogen, an alkyl group (e.g., alkyl groups having 1 to
8 carbon atoms, such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, n-pentyl,
isopentyl, hexyl, heptyl and octyl), a nitro group or a sulfonic group.
[0029] Ki
n+ represents an organic ammonium ion; m represents 1 or 2, and n represents 1 or 2.
[0030] Referring to the laser ray transmitting colored polyolefin resin composition of the
present invention, it is preferable that in Formula (1) above, at least one of R
4 to R
8 be a sulfonic group, and also at least one of R
9 to R
13 be a sulfonic group.
[0032] In Formula (1) above, Ki
n+ is an organic ammonium ion that constitutes the organic ammonium component of an
anthraquinone salt forming dye in the present invention, and may be one represented
by Formula (2) or (3) below.
[0033] In Formula (2) above, each of R
14 through R
17 independently represents,
hydrogen,
an alkyl group (e.g., alkyl groups having 1 to 12 carbon atoms that may be branched,
such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, n-pentyl,
isopentyl, tert-pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl and dodecyl),
a cycloalkyl group (e.g., cycloalkyl groups having 3 to 8 carbon atoms, such as cyclopropyl,
cyclopentyl, cyclohexyl and cycloheptyl, or dihydroaziethylamine residues),
an alkoxyalkyl group (e.g., alkoxyalkyl groups having 2 to 20 carbon atoms, such as
[methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or octyloxy, etc.]-[methyl,
ethyl, propyl, butyl, pentyl, or octyl, etc.] etc., i.e., ethoxymethyl, methoxyethyl,
etc.),
an alkanol group (e.g. -CH2OH, -C2H4OH, -C3H6OH, etc.),
an aryl group (e.g., phenyl, lower-alkyl-substituted phenyls, halogenated phenyls,
naphthyl, aminonaphthyls) having or not having a substituent [e.g., amino groups,
lower (1 to 4 carbon atoms) alkyl groups, halogens such as Cl and Br],
an aralkyl group (e.g., benzyl group, a -methylbenzyl group, α,α-dimethylbenzyl group,
α-butylbenzyl group, phenethyl group, naphthylalkyl groups [e.g., naphthylmethyl,
naphthylethyl, etc.]) having or not having a substituent [e.g., amino groups, alkyl
groups having 1 to 4 carbon atoms, halogens such as Cl and Br], or
a group represented by Formula (C) below.
[0034] In Formula (3) above, each of R
18 to R
21 independently represents hydrogen or an aryl group (e.g., phenyl, lower-alkyl-substituted
phenyls, halogenated phenyls, naphthyl, aminonaphthyls) having or not having a substituent
[e.g., amino group, lower (1 to 4 carbon atoms) alkyl groups, halogens such as Cl
and Br].
[0035] Organic ammonium components represented by Formulas (2) and (3) above can be obtained
from organic amines exemplified below, which, however, are not to be construed as
limiting the present invention.
[0036] Specifically, there may be mentioned aliphatic amines such as hexylamine, pentylamine,
octylamine, 2-ethylhexylamine, di-(2-ethylhexyl)amine and dodecylamine; alicyclic
amines such as cyclohexylamine, di-cyclohexylamine and dihydroaziethylamine; alkoxyalkylamines
such as 3-propoxypropylamine, di-(3-ethoxypropyl)amine, 3-butoxypropylamine, octoxypropylamine
and 3-(2-ethylhexyloxy)propylamine; naphthylamines such as α-naphthylamine, β-naphthylamine,
1,2-naphthylenediamine, 1,5-naphthylenediamine and 1,8-naphthylenediamine; naphthylalkylamines
such as 1-naphthylmethylamine; alkanol-group-containing amines such as N-cyclohexylethanolamine,
N-dodecylethanolamine and N-dodecylimino-di-ethanol; and guanidines (derivatives)
such as 1,3-diphenylguanidine, 1-o-tolylguanidine and di-o-tolylguanidine.
[0037] Of the organic ammonium components represented by Formula (2) above, those that are
particularly preferred are shown in Table 1.
Table 1
|
R14 |
R15 |
R16 |
R17 |
S-1 |
H |
H |
H |
|
S-2 |
H |
H |
H |
-(CH2)3-O-CH2(C2H5)CKC4H9 |
S-3 |
H |
H |
H |
|
[0038] Of the organic ammonium components represented by Formula (3) above, those that are
particularly preferred are shown in Table 2.
[0039] In particular, aromatic guanidines as shown in Table 2 are unlikely to volatilize
under heating in an extruding machine, an injection molding machine and the like.
Hence, of the anthraquinone salt forming dyes represented by Formula (1) above, those
having such an aromatic guanidine as the organic ammonium component are unlikely to
decompose, even through processes such as thermal melting during molding, and exhibit
excellent dispersibility in the molded product. As a result, the molded product obtained
is excellent in laser ray transmission.
[0040] The anthraquinone salt forming dye used in the present invention has a color such
as blue, purple or green. As a colorant for the laser ray transmitting colored polyolefin
resin composition of the present invention, there may be used an anthraquinone salt
forming dyes having various colors alone, or two species or more of such salt forming
dyes in combination. Also, as a colorant for the laser ray transmitting colored polyolefin
resin composition of the present invention, there may be used one species or two species
or more of pigments or dyes that have an absorption band only outside the visible
light absorption band of the anthraquinone salt forming dye or have an absorption
band outside the visible light in addition to visible light absorption band, and that
allows light transmission in the wavelength band of laser ray (wavelength from 800
nm to 1200 nm), along with the aforementioned anthraquinone salt forming dye. By blending
dyes or pigments having a color such as yellow or red, that are other colorants offering
good laser transmission as described above, it is possible to impart various colors.
For example, by combining a purple dye among the aforementioned anthraquinone salt
forming dyes and another yellow colorant, it is possible to impart a black color.
Of the laser ray transmitting colored polyolefin resin compositions, black resin compositions
are industrially important.
[0041] As examples of such other colorants that are capable of imparting colors to resin,
there may be mentioned azo salt forming dyes and/or anthrapyridone dyes that exhibit
chromatic colors such as yellow, orange and red, and that transmit laser.
[0042] As specific examples of acid dyes corresponding to the anion components of azo salt
forming dyes that can be used along with an anthraquinone salt forming dye of Formula
(1) in the laser ray transmitting colored polyolefin resin composition of the present
invention, the following examples may be mentioned. Red acid dyes such as C.I. Acid
Red 1, 3, 4, 5, 7, 8, 9, 10, 12, 13, 14, 17, 18, 23, 24, 26, 27, 30, 33, 34, 35, 37,
40, 41, 54, 60, 66, 70, 73, 74, 88, 97, 102, 112, 115, 135, 137, 138, 141, 143, 144,
148, 150, 151, 176, 231 and 266; and yellow acid dyes such as C.I. Acid Yellow 4,
9, 17, 18, 19, 23, 36, 41, 42, 49, 105, 199, 200 and 219. However, the present invention
is not limited by these examples.
[0043] As specific examples of acid dyes corresponding to the anion components of anthrapyridone
salt forming dyes that can be used along with an anthraquinone salt forming dye of
Formula (1) in the laser ray transmitting colored polyolefin resin composition of
the present invention, there may be mentioned red acid dyes such as C.I. Acid Red
80, 81, 82 and 143. However, the present invention is not limited by these examples.
[0044] The amount of colorant used in the laser ray transmitting colored polyolefin resin
composition of the present invention may, for example, be 0.01 to 10% by weight relative
to polyolefin resin. The amount is preferably 0.1 to 5% by weight, more preferably
0.1 to 1% by weight.
[0045] A master batch (high-concentration molded product) of the laser ray transmitting
colored polyolefin resin composition of the present invention is obtained by, for
example, blending polyolefin resin powder or pellets as a master batch base and a
colorant containing at least an anthraquinone salt forming dye of Formula (1) above
in a tumbler or super-mixer and the like, and then pelletizing or coarsely granulating
it by thermal melting in an extruder, batch-wise kneader, roll kneader, or the like.
A master batch can also be obtained by, for example, adding the aforementioned colorant
to polyolefin resin for a master batch base while remaining in solution after synthesis,
and then removing the solvent.
[0046] By blending the thus-obtained colored pellets or coarsely granulated colorant (this
colorant form is referred to as master batch in the present invention) with a polyolefin
resin and molding this by a conventional method, it is possible to obtain a more uniform
laser ray transmitting resin part of excellent laser transmission quality. In particular,
when using a black mixed colorant of a combination of an anthraquinone salt forming
dye and a plurality of colorants, this effect is remarkable.
[0047] As such, the master batch may contain the aforementioned colorant at 1 to 30% by
weight, for example, relative to the amount of polyolefin resin. The content ratio
is preferably 5 to 15% by weight.
[0048] T
colored resin /T
noncolored resin, i.e., the ratio of T
colored resin, the transmittance for a laser ray having a wavelength of 940 nm in the laser ray
transmitting colored polyolefin resin composition of the present invention, and T
noncolored resin' the transmittance for a laser ray having a wavelength of 940 nm in a noncolored
resin of the same but without a colorant, is preferably 0.8 to 1.2.
[0049] The laser ray transmitting colored polyolefin resin composition of the present invention
may contain appropriate amounts of various reinforcing materials according to its
application and intended use. These reinforcing materials are not particularly limited,
as long as it is usable for ordinary reinforcement of synthetic resins. For example,
glass fiber, carbon fiber, other inorganic fibers, and organic fibers (aramid, polyphenylene
sulfide, nylon, polyester, liquid crystal polymer, etc.), etc. can be used, with preference
given to glass fiber for reinforcement of resins that require transparency. The fiber
length of glass fiber is preferably 2 to 15 mm and the fiber diameter is preferably
1 to 20 µm. The form of glass fiber is not subject to limitation, and may be of any
one, e.g., roving or milled fiber. These glass fibers may be used singly or in combination
of two or more kinds. Their content is preferably 5 to 120% by weight relative to
100% by weight of polyolefin resin. If the content is less than 5% by weight, a sufficient
glass fiber-reinforcing effect is unlikely to be attained; if the content exceeds
120% by weight, moldability is likely to decrease. Their content is preferably 10
to 60% by weight, particularly preferably 20 to 50% by weight.
[0050] The laser ray transmitting colored polyolefin resin composition of the present invention
may contain appropriate amounts of various fillers according to its application and
intended use. There can be used, for example, tabular fillers such as mica, sericite
and glass flake, silicates such as talc, kaolin, clay, wollastonite, bentonite, asbestos
and alumina silicate, metal oxides such as alumina, silicon oxide, magnesium oxide,
zirconium oxide and titanium oxide, carbonates such as calcium carbonate, magnesium
carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, and particulate
fillers such as glass beads, ceramic beads, boron nitride and silicon carbide. As
an example of a preferred filler in the present invention, there may be mentioned
talc. Although useful particle diameters of the filler range widely, from as fine
as 0.03 µ m to about 100 µm, those having particle diameters of 0.03 to 10 µm are
preferred for the laser ray transmitting colored polyolefin resin composition and
method of laser welding of the present invention. The filler content is preferably
5 to 50% by weight relative to 100% by weight of polyolefin resin. If the content
is less than 5% by weight, a sufficient effect for a filler is unlikely to be attained;
if the content exceeds 50% by weight, laser transmission decreases considerably. The
content is preferably 10 to 50% by weight, particularly preferably 10 to 40% by weight.
[0051] The laser ray transmitting colored polyolefin resin composition of the present invention
may also be formulated with various additives as necessary. Such additives include,
for example, auxochromic agents, dispersing agents, stabilizers, plasticizers, quality-improving
agents, ultraviolet absorbents or light stabilizers, antioxidants, antistatic agents,
lubricants, mold-releasing agents, crystallization promoters, crystal nucleating agents,
and flame retardants.
[0052] The laser ray transmitting colored polyolefin resin composition of the present invention
is obtained by blending raw materials by an optionally chosen method of blending.
It is generally preferable that these blending ingredients be homogenized to the maximum
possible extent. Specifically, for example, all raw materials are blended and homogenized
in a mechanical mixer such as a blender, kneader, Banbury mixer, roll mixer or extruder
to yield a colored polyolefin resin composition. Alternatively, after some raw materials
are blended in a mechanical mixer, the remaining ingredients are added, followed by
further blending and homogenization, to yield a resin composition. Additionally, previously
dry-blended raw materials may be kneaded and homogenized in a molten state in a heated
extruder, then extruded into a needle, which needle is then cut into desired length
to yield a colored granular resin composition (colored pellets).
[0053] Molding of the laser ray transmitting colored polyolefin resin composition of the
present invention can be achieved by various procedures in common use. For example,
the laser ray transmitting colored polyolefin resin composition of the present invention
can be molded using colored pellets in a processing machine such as an extruder, injection
molding machine or roll mill, and can also be molded by blending polyolefin resin
pellets or powder, a milled colorant, and where necessary various additives, in an
appropriate mixer, and molding this blend using a processing machine. Any commonly
used method of molding can be adopted, e.g., injection molding, extrusion molding,
compression molding, foaming molding, blow molding, vacuum molding, injection blow
molding, rotation molding, calender molding, and solution casting. By such molding,
laser ray transmitting materials in various shapes can be obtained.
[0054] The method of laser welding of the present invention comprises welding a portion
of contact of a laser ray transmitting material comprising the aforementioned laser
ray transmitting colored thermoplastic resin composition and a laser ray absorbing
material by irradiating laser ray so that the laser ray transmitting material transmits
the laser ray and the laser ray is absorbed in the laser ray absorbing material with
the laser ray transmitting material and the laser ray absorbing material in contact
with each other.
[0055] As examples of combinations of resins that permit laser welding in the method of
laser welding of the present invention, there may be mentioned a combination of polypropylene
resins, a combination of polyethylene resins, a combination of a polypropylene resin
and a polyethylene resin, a combination of a polypropylene resin and a thermoplastic
elastomer (particularly an olefin thermoplastic elastomer), and a combination of a
polypropylene resin and a thermoplastic resin (e.g., polyamide and polycarbonate).
[0056] Generally, advantages of laser welding include increased degrees of freedom for the
shapes of the molds for the molded resin products of laser ray transmitting material
and laser ray absorbing material to be welded because of the capability of 3-dimensional
welding, improved appearance because of freedom from burrs on the welded surface unlike
in vibration welding, and applicability to electronic components because of freedom
from vibration and wear dust. Conversely, its disadvantages include the necessity
of pre-investment in equipment known as laser welding machine, and possible gap formation
between the parts for welding, due to sink during the molding of the laser ray transmitting
material and laser ray absorbing material to be welded, both of which are made of
resin. The problem with this gap, in particular, is of greatest concern in performing
laser welding; there are many cases where a jig for fixture such as a clamp is made
on a case-by-case basis to adapt it to the shapes of the parts to be welded. It is
known that if a gap of 0.02 mm occurs, welding strength halves compared to the gap-free
state, and that welding fails if the gap is 0.05 mm or more.
[0057] Available laser welding machines include the scanning type, in which laser moves,
the masking type, in which the parts to be welded move, and the type in which laser
rays are irradiated to the parts to be welded from multiple directions simultaneously.
It is the scanning type which is drawing attention from the automobile industry, with
a scanning speed of 5 m/min serving as the criterion for production tact time.
[0058] Because laser welding relies on the conversion of light energy of laser to heat energy,
welding performance is considerably influenced by laser welding conditions. Generally,
the amount of heat produced by irradiated laser on the absorbent part surface can
be calculated by the equation below:
[0059] To increase production efficiency, the scanning speed must be increased; to achieve
this, a laser welding machine of the high output type is necessary.
[0060] Additionally, to increase welding strength, some heat on the surface of the laser
absorbing part is necessary. This heat must be determined by combining various conditions
such as increased output setting, decreased scanning speed, and decreased spot diameter.
Since too great surface heat provided by laser affects the appearance of the welded
portion and, in the extreme case, causes the laser absorbing part to smoke, laser
welding condition settings are important and the laser transmittance of the laser
ray transmitting resin material to be welded is of paramount importance. Considering
the above-described conditions, it is preferable that in the method of laser welding
of the present invention, a contact portion of a laser ray transmitting material and
a laser ray absorbing material be welded in a state that satisfies Formula (A). By
doing so, a welded product having a practically unproblematic welding strength is
obtained.
Where
Q: amount of heat on surface of laser ray absorbing material (J/mm2)
P: output (W) of laser that laser ray transmitting material transmits
S: laser scanning speed (mm/sec)
φ : spot diameter of laser (mm)
[0061] It is preferable that the laser ray absorbing material comprise a laser ray absorbing
colored resin composition incorporating carbon black and/or another laser ray absorbent,
for example, as a laser ray absorbing black colorant.
[0062] As substances that can be used as both the aforementioned black colorant and laser
ray absorbent, there may be mentioned carbon black, nigrosine, aniline black and so
on. As examples of other laser ray absorbents, there may be mentioned phthalocyanine,
naphthalocyanine, perilene, quaterylene, metal complexes, squaric acid derivatives,
immonium dyes, polymethine, etc.;
two or more thereof may be blended to obtain a black laser ray absorbent. Furthermore,
it is also possible to use the aforementioned laser ray transmitting colorant and
laser ray absorbent in combination. A preferred laser absorbing black colorant is
a combination of carbon black and nigrosine.
[0063] As the carbon black with good laser absorbability, there may be mentioned those 15
to 100 nm (preferably 15 to 50 nm) in primary particle diameter, and those 30 to 500
m
2/g (preferably 100 to 300 m
2/g) in BET specific surface area.
[0064] The amount of colorant used in such a laser ray absorbing colored resin composition
may be, for example, 0.01 to 10% by weight relative to polyolefin resin, and is preferably
0.05 to 5% by weight. The laser ray absorbing material can be produced in the same
manner as the laser ray transmitting material except for the containment of a laser
ray absorbent.
[0065] As examples of major applications of the laser ray transmitting colored polyolefin
resin composition and method of laser welding of the present invention, there may
be mentioned automobile parts. More specifically, there may be mentioned, for example,
instrument panels in interiors and resonators (mufflers) in engine rooms. Conventionally,
use of adhesives has been difficult in joining polyolefin resin parts; to achieve
their joining, special procedures such as surface treatment have been necessary. When
laser welding is used, there is no need for pretreatment, alloying of resin and the
like; laser welding can be said to surpass adhesives also in terms of strength and
recyclability.
EXAMPLES
[0066] The present invention is hereinafter described in more detail by means of, but is
not limited to, the following examples.
[0067] Referring to Table 3, the colorants prepared in Production Examples 1 to 8 were used
in the respective Examples, and the colorants prepared in Comparative Production Examples
1 to 8 were used in the respective Comparative Examples. All these colorants were
single salt forming dyes or mixed dyes of two or more kinds of salt forming dyes.
The anionic components shown as the Example Compounds above correspond to the acid
dyes for the respective Production Examples, and the organic ammonium components shown
in Table 1 or 2 correspond to the organic amines for the respective Production Examples.
The salt forming dyes of each of C.I. Acid Red 266 (monoazo acid dye), C.I. Acid Yellow
49 (monoazo acid dye), C.I. Acid Red 143 (anthrapyridone acid dye), C.I. Acid Red
97 (disazo acid dye), C.I. Acid Red 144 (disazo acid dye), C.I. Acid Yellow 42 (monoazo
acid dye), C.I. Acid Violet 43 (anthraquinone acid dye), C.I. Acid Blue 41 (anthraquinone
acid dye), C.I. Acid Blue 62 (anthraquinone acid dye) and C.I. Acid Blue 260 (anthraquinone
acid dye) and each organic amine in Production Examples 4 to 8 and Comparative Production
Examples 1 to 8 were obtained by a salt-forming reaction of each acid dye and each
organic amine.
[0068] Each of the colorants of Production Examples 1 to 3 and Comparative Production Examples
1 to 4 comprises a single salt forming dye, whereas the colorants of Production Examples
4 to 8 and Comparative Production Examples 5 to 8 are black colorants prepared by
blending a plurality of salt forming dyes according to the respective content ratios
by weight shown in the content ratio column using a simple mechanical mixer.
[0069] For example, the colorant of Production Example 1 was produced as described below.
First, 10 g of an anthraquinone acid dye represented by Example Compound (1)-1 was
dispersed in 500 ml of water. Separately, 5 mg of hydrochloric acid and 7 g of the
organic amine S-4 were dissolved in 150 ml of water. This solution was added drop
by drop to the dispersion liquid of said anthraquinone acid dye at room temperature,
and the reaction was carried out with stirring at 40 to 45°C for 1 hour. Subsequently,
the temperature was increased to 60 to 70°C to make the reaction product particulate,
and the reaction mixture was adjusted to a pH of 6.5 to 7.5 and stirred for 1 hour.
The reaction mixture was filtered and the cake filtered out was washed with water,
to yield 12.0 g (yield 75%) of an anthraquinone salt forming dye.
Table 3
|
Acid dye |
Organic amine |
Content ratio |
Production Example 1 |
Example Compound (1)-1 |
S-4 |
- |
Production Example 2 |
Example Compound (1)-2 |
S-4 |
- |
Production Example 3 |
Example Compound (1)-4 |
S-4 |
- |
Production Example 4 |
Example Compound (1)-1 |
S-4 |
5 |
C.I. Acid Red 266 |
S-4 |
3 |
C.I. Acid Yellow 49 |
S-4 |
2 |
Production Example 5 |
Example Compound (1)-2 |
S-4 |
2 |
C.I. Acid Red 143 |
S-4 |
1 |
Production Example 6 |
Example Compound (1)-3 |
S-4 |
1 |
C.I. Acid Red 97 |
S-5 |
1 |
Production Example 7 |
Example Compound (1)-1 |
S-4 |
2 |
C.I. Acid Red 144 |
S-4 |
2 |
C.I. Acid Yellow 42 |
S-1 |
3 |
Production Example 8 |
Example Compound (1)-4 |
S-4 |
5 |
C.I. Acid Yellow 42 |
S-4 |
1 |
Comparative Production Example 1 |
C.I. Acid Violet 43 |
S-4 |
- |
Comparative Production Example 2 |
C.I. Acid Blue 41 |
S-4 |
- |
Comparative Production Example 3 |
C.I. Acid Blue 62 |
S-4 |
- |
Comparative Production Example 4 |
C.I. Acid Blue 260 |
S-4 |
- |
Comparative Production Example 5 |
C.I. Acid Blue 62 |
S-4 |
5 |
C.I. Acid Red 266 |
S-4 |
2 |
C.I. Acid Yellow 42 |
S-4 |
1 |
Comparative Production Example 6 |
C.I. Acid Violet 43 |
S-4 |
3 |
C.I. Acid Yellow 49 |
S-4 |
1 |
Comparative Production Example 7 |
C.I. Acid Blue 41 |
S-3 |
5 |
C.I. Acid Red 266 |
S-3 |
3 |
C.I. Acid Yellow 49 |
S-3 |
2 |
Comparative Production Example 8 |
C.I. Acid Blue 260 |
S-4 |
5 |
C.I. Acid Red 266 |
S-4 |
3 |
C.I. Acid Yellow 42 |
S-4 |
2 |
Example 1
[0070] Fiber-reinforced polypropylene resin....400 g (manufactured by Japan Polychem, product
number: HG30U)
Colorant of Production Example 1....0.80 g
[0071] The above ingredients were placed in a stainless steel tumbler and mixed with stirring
for 1 hour. The blend obtained was injection-molded by an ordinary method at a cylinder
temperature of 220°C and a mold temperature of 40°C using an injection molding machine
(manufactured by Toyo Machinery & Metal Co., Ltd., product number: Si-50); a uniformly
colored blue test piece having good appearance and surface gloss was obtained.
Example 2
[0072] Fiber-reinforced polypropylene resin....400 g (manufactured by Japan Polychem, product
number: HG30U)
Colorant of Production Example 2....0.80 g
[0073] The above ingredients were placed in a stainless steel tumbler and mixed with stirring
for 1 hour. The blend obtained was injection-molded by an ordinary method at a cylinder
temperature of 220°C and a mold temperature of 40°C using an injection molding machine
(manufactured by Toyo Machinery & Metal Co., Ltd., product number: Si-50); a uniformly
colored green test piece having good appearance and surface gloss was obtained.
Example 3
[0074] Fiber-reinforced polypropylene resin....400 g (manufactured by Japan Polychem, product
number: HG30U)
Colorant of Production Example 3....0.80 g
[0075] The above ingredients were placed in a stainless steel tumbler and mixed with stirring
for 1 hour. The blend obtained was injection-molded by an ordinary method at a cylinder
temperature of 220°C and a mold temperature of 40°C using an injection molding machine
(manufactured by Toyo Machinery & Metal Co., Ltd., product number: Si-50); a uniformly
colored purple test piece having good appearance and surface gloss was obtained.
Example 4
[0076] Fiber-reinforced polypropylene resin....400 g (manufactured by Japan Polychem, product
number: HG30U)
Colorant of Production Example 4....1.20 g
[0077] The above ingredients were placed in a stainless steel tumbler and mixed with stirring
for 1 hour. The blend obtained was injection-molded by an ordinary method at a cylinder
temperature of 220°C and a mold temperature of 40°C using an injection molding machine
(manufactured by Toyo Machinery & Metal Co., Ltd., product number: Si-50); a uniformly
colored black test piece having good appearance and surface gloss was obtained.
Example 5
[0078] Fiber-reinforced polypropylene resin....400 g (manufactured by Japan Polychem, product
number: HG30U)
Colorant of Production Example 5....1.20 g
[0079] The above ingredients were placed in a stainless steel tumbler and mixed with stirring
for 1 hour. The blend obtained was injection-molded by an ordinary method at a cylinder
temperature of 220°C and a mold temperature of 40°C using an injection molding machine
(manufactured by Toyo Machinery & Metal Co., Ltd., product number: Si-50); a uniformly
colored black test piece having good appearance and surface gloss was obtained.
Example 6
[0080] Fiber-reinforced polypropylene resin....400 g (manufactured by Japan Polychem, product
number: HG30U)
Colorant of Production Example 6....1.20 g
[0081] The above ingredients were placed in a stainless steel tumbler and mixed with stirring
for I hour. The blend obtained was injection-molded by an ordinary method at a cylinder
temperature of 220°C and a mold temperature of 40°C using an injection molding machine
(manufactured by Toyo Machinery & Metal Co., Ltd., product number: Si-50); a uniformly
colored black test piece having good appearance and surface gloss was obtained.
Example 7
[0082] Fiber-reinforced polypropylene resin....400 g (manufactured by Japan Polychem, product
number: HG30U)
Colorant of Production Example 7....1.20 g
[0083] The above ingredients were placed in a stainless steel tumbler and mixed with stirring
for I hour. The blend obtained was injection-molded by an ordinary method at a cylinder
temperature of 220°C and a mold temperature of 40°C using an injection molding machine
(manufactured by Toyo Machinery & Metal Co., Ltd., product number: Si-50); a uniformly
colored black test piece having good appearance and surface gloss was obtained.
Example 8
[0084] Fiber-reinforced polypropylene resin....400 g (manufactured by Japan Polychem, product
number: HG30U)
Colorant of Production Example 8....1.20 g
[0085] The above ingredients were placed in a stainless steel tumbler and mixed with stirring
for 1 hour. The blend obtained was injection-molded by an ordinary method at a cylinder
temperature of 220°C and a mold temperature of 40°C using an injection molding machine
(manufactured by Toyo Machinery & Metal Co., Ltd., product number: Si-50); a uniformly
colored black test piece having good appearance and surface gloss was obtained.
Example 9
[0086] Polypropylene resin (not reinforced)....900 g (manufactured by Japan Polychem, product
number: BC05B)
Colorant of Production Example 8....100 g
[0087] The above ingredients were placed in a stainless steel tumbler and mixed with stirring
for 1 hour. The blend obtained was mixed in a molten state at a cylinder temperature
of 220°C using a single-shaft extruder (manufactured by Enpura Sangyo, product number:
E30SV). Subsequently, it was cooled in a water chamber and then cut using a pelletizer
and subjected to a drying process to yield a black master batch.
Fiber-reinforced polypropylene resin....384 g (manufactured by Japan Polychem, product
number: HG30U)
Black master batch....12 g
[0088] The above ingredients were placed in a stainless steel tumbler and mixed with stirring
for 20 minutes. The blend obtained was injection-molded by an ordinary method at a
cylinder temperature of 220°C and a mold temperature of 40 °C using an injection molding
machine (manufactured by Toyo Machinery & Metal Co., Ltd., product number: Si-50);
a uniformly colored black test piece having good appearance and surface gloss was
obtained.
Example 10
[0089] Low-density polyethylene resin....400 g (manufactured by Japan Polychem, product
number: LC604)
Colorant of Production Example 8....1.20 g
[0090] The above ingredients were placed in a stainless steel tumbler and mixed with stirring
for I hour. The blend obtained was injection-molded by an ordinary method at a cylinder
temperature of 180°C and a mold temperature of 40°C using an injection molding machine
(manufactured by Toyo Machinery & Metal Co., Ltd., product number: Si-50); a uniformly
colored black test piece having good appearance and surface gloss was obtained.
Example 11
[0091] High-density polyethylene resin....400 g (manufactured by Japan Polychem, product
number: HJ290)
Colorant of Production Example 8....1.20 g
[0092] The above ingredients were placed in a stainless steel tumbler and mixed with stirring
for 1 hour. The blend obtained was injection-molded by an ordinary method at a cylinder
temperature of 210°C and a mold temperature of 40°C using an injection molding machine
(manufactured by Toyo Machinery & Metal Co., Ltd., product number: Si-50); a uniformly
colored black test piece having good appearance and surface gloss was obtained.
Example 12
[0093] Polyolefin cross-linked thermoplastic elastomer....400 g (manufactured by Advanced
Elastomer Systems Japan, product number: Santoprene 821 1-65)
Colorant of Production Example 1....0.40 g
[0094] The above ingredients were placed in a stainless steel tumbler and mixed with stirring
for 1 hour. The blend obtained was injection-molded by an ordinary method at a cylinder
temperature of 200°C and a mold temperature of 40°C using an injection molding machine
(manufactured by Toyo Machinery & Metal Co., Ltd., product number: Si-50); a uniformly
colored blue test piece having good appearance and surface gloss was obtained.
Example 13
[0095] Polypropylene resin (not reinforced)....790 g (manufactured by Japan Polychem, product
number: BC05B)
Colorant of Production Example 8....10 g
Talc....200 g
[0096] The above ingredients were mixed with stirring in a high-speed mixer for 20 minutes.
The blend obtained was mixed in a molten state at a cylinder temperature of 220°C
using a single-shaft extruder (manufactured by Enpura Sangyo, product number: E30SV).
Subsequently, it was cooled in a water chamber and then cut using a pelletizer and
subjected to a drying process to yield black pellets.
[0097] Subsequently, they were injection-molded by an ordinary method at a cylinder temperature
of 200°C and a mold temperature of 40°C using an injection molding machine (manufactured
by Toyo Machinery & Metal Co., Ltd., product number: Si-50); a uniformly colored black
test piece having good appearance and surface gloss was obtained.
Comparative Example 1_
[0098] Fiber-reinforced polypropylene resin....400 g (manufactured by Japan Polychem, product
number: HG30U)
Colorant of Comparative Production Example 1....0.80 g
[0099] The above ingredients were placed in a stainless steel tumbler and mixed with stirring
for 1 hour. The blend obtained was injection-molded by an ordinary method at a cylinder
temperature of 220°C and a mold temperature of 40°C using an injection molding machine
(manufactured by Toyo Machinery & Metal Co., Ltd., product number: Si-50); a purple
test piece was obtained.
Comparative Example 2
[0100] Fiber-reinforced polypropylene resin....400 g (manufactured by Japan Polychem, product
number: HG30U)
Colorant of Comparative Production Example 2....0.80 g
[0101] The above ingredients were placed in a stainless steel tumbler and mixed with stirring
for 1 hour. The blend obtained was injection-molded by an ordinary method at a cylinder
temperature of 220°C and a mold temperature of 40°C using an injection molding machine
(manufactured by Toyo Machinery & Metal Co., Ltd., product number: Si-50); a blue
test piece was obtained.
Comparative Example 3
[0102] Fiber-reinforced polypropylene resin....400 g (manufactured by Japan Polychem, product
number: HG30U)
Colorant of Comparative Production Example 3....0.80 g
[0103] The above ingredients were placed in a stainless steel tumbler and mixed with stirring
for 1 hour. The blend obtained was injection-molded by an ordinary method at a cylinder
temperature of 220°C and a mold temperature of 40°C using an injection molding machine
(manufactured by Toyo Machinery & Metal Co., Ltd., product number: Si-50); a blue
test piece was obtained.
Comparative Example 4
[0104] Fiber-reinforced polypropylene resin....400 g (manufactured by Japan Polychem, product
number: HG30U)
Colorant of Comparative Production Example 4....0.80 g
[0105] The above ingredients were placed in a stainless steel tumbler and mixed with stirring
for 1 hour. The blend obtained was injection-molded by an ordinary method at a cylinder
temperature of 220°C and a mold temperature of 40°C using an injection molding machine
(manufactured by Toyo Machinery & Metal Co., Ltd., product number: Si-50); a blue
test piece was obtained.
Comparative Example 5
[0106] Fiber-reinforced polypropylene resin....400 g (manufactured by Japan Polychem, product
number: HG30U)
Colorant of Comparative Production Example 5....0.80 g
[0107] The above ingredients were placed in a stainless steel tumbler and mixed with stirring
for I hour. The blend obtained was injection-molded by an ordinary method at a cylinder
temperature of 220°C and a mold temperature of 40°C using an injection molding machine
(manufactured by Toyo Machinery & Metal Co., Ltd., product number: Si-50); a black
test piece was obtained.
Comparative Example 6
[0108] Fiber-reinforced polypropylene resin....400 g (manufactured by Japan Polychem, product
number: HG30U)
Colorant of Comparative Production Example 6....0.80 g
[0109] The above ingredients were placed in a stainless steel tumbler and mixed with stirring
for 1 hour. The blend obtained was injection-molded by an ordinary method at a cylinder
temperature of 220°C and a mold temperature of 40°C using an injection molding machine
(manufactured by Toyo Machinery & Metal Co., Ltd., product number: Si-50); a black
test piece was obtained.
Comparative Example 7
[0110] Fiber-reinforced polypropylene resin....400 g (manufactured by Japan Polychem, product
number: HG30U)
Colorant of Comparative Production Example 7....1.20 g
[0111] The above ingredients were placed in a stainless steel tumbler and mixed with stirring
for 1 hour. The blend obtained was injection-molded by an ordinary method at a cylinder
temperature of 220°C and a mold temperature of 40°C using an injection molding machine
(manufactured by Toyo Machinery & Metal Co., Ltd., product number: Si-50); a black
test piece was obtained.
Comparative Example 8
[0112] Fiber-reinforced polypropylene resin....400 g (manufactured by Japan Polychem, product
number: HG30U)
Colorant of Comparative Production Example 8....1.20 g
[0113] The above ingredients were placed in a stainless steel tumbler and mixed with stirring
for 1 hour. The blend obtained was injection-molded by an ordinary method at a cylinder
temperature of 220°C and a mold temperature of 40°C using an injection molding machine
(manufactured by Toyo Machinery & Metal Co., Ltd., product number: Si-50); a black
test piece was obtained.
Physical property assessments
[0114] The laser ray transmitting colored polyolefin resin compositions obtained in Examples
1 to 8 and Comparative Examples 1 to 8 and similarly molded uncolored polyolefin resin
(PP) test pieces were subjected to physical property assessments by the methods described
below. The results are shown in Tables 4 and 5 below.
(1) Determination of transmittance
[0115] Each test piece was set to a spectrophotometer (manufactured by JASCO Corporation,
product number: V-570 model), and its transmittance was determined over a wavelength
range of λ = 400 to 1200 nm. Tables 4 and 5 show the transmittances of respective
test pieces for semiconductor laser ray at a wavelength of 940 nm.
(2) Anti-sublimation test and assessment
[0116] A test piece with a white PET (polyethylene terephthalate resin) film applied thereto
was placed in an oven and allowed to stand at 160°C for 3 hours. Thereafter, the PET
film was removed from the test piece and applied to a colorless transparent OHP (overhead
projector) sheet to facilitate observation. If the dye had not migrated to the PET
film, the dye was judged to have anti-sublimation quality.
(3) Heat resistance test and assessment
[0117] In the injection molding in Examples 1 to 8 and Comparative Examples 1 to 8 above,
a blend of ingredients was subjected to an ordinary shot, and thereafter the remaining
portion of the blend was retained in the cylinder at 220°C for 15 minutes; injection
molding was then conducted to yield test pieces.
[0118] If the discoloration/fading of the color of the test piece obtained after the retainment
in the cylinder for 15 minutes had not advanced compared to the color of the test
piece obtained by an ordinary shot, it was judged to be resistant to heat.
(4) Anti-bleeding test and assessment
[0119] Each of the test pieces obtained in Examples 1 to 8 and Comparative Examples 1 to
8 above and a white test piece colored with titanium oxide were superposed in the
direction of thickness, and was allowed to stand at 80°C for 100 hours under a pressure
of 200 g (1.96 N)/cm
2 exerted in the direction of superposition. Subsequently, degree of colorant migration
to the white test piece was examined. If the colorant had not migrated to the white
test piece, the test piece was judged to have anti-bleeding quality.
(5) Preparation of laser absorbing test pieces for laser welding test and laser welding
test
[0120] laser absorbing test pieces (laser ray absorbing materials) incorporating a polyolefin
resin were prepared as described below.
Fiber-reinforced polypropylene resin....400 g (manufactured by Japan Polychem, product
number: HG30U)
Carbon black....0.80 g
[0121] The above ingredients were placed in a stainless steel tumbler and mixed with stirring
for 1 hour. The blend obtained was injection-molded by an ordinary method at a cylinder
temperature of 220°C and a mold temperature of 40°C using an injection molding machine
(manufactured by Toyo Machinery & Metal Co., Ltd., product number: Si-50); a uniformly
colored black laser absorbing test piece having good appearance and surface gloss
was obtained.
Low-density polyethylene resin....400 g (manufactured by Japan Polychem, product number:
LC604)
Carbon black....0.80 g
[0122] The above ingredients were placed in a stainless steel tumbler and mixed with stirring
for 1 hour. The blend obtained was injection-molded by an ordinary method at a cylinder
temperature of 180°C and a mold temperature of 40°C using an injection molding machine
(manufactured by Toyo Machinery & Metal Co., Ltd., product number: Si-50); a uniformly
colored black test piece having good appearance and surface gloss was obtained.
High-density polyethylene resin....400 g (manufactured by Japan Polychem, product
number: HJ290)
Carbon black....0.80 g
[0123] The above ingredients were placed in a stainless steel tumbler and mixed with stirring
for 1 hour. The blend obtained was injection-molded by an ordinary method at a cylinder
temperature of 210°C and a mold temperature of 40°C using an injection molding machine
(manufactured by Toyo Machinery & Metal Co., Ltd., product number: Si-50); a uniformly
colored black test piece having good appearance and surface gloss was obtained.
Polyolefin cross-linked thermoplastic elastomer....400 g (manufactured by Advanced
Elastomer Systems Japan, product number: Santoprene 8211-65)
Carbon black....0.40 g
[0124] The above ingredients were placed in a stainless steel tumbler and mixed with stirring
for 1 hour. The blend obtained was injection-molded by an ordinary method at a cylinder
temperature of 200°C and a mold temperature of 40°C using an injection molding machine
(manufactured by Toyo Machinery & Metal Co., Ltd., product number: Si-50); a uniformly
colored black test piece having good appearance and surface gloss was obtained.
Talc-containing polypropylene resin....400 g
Carbon black....2.00 g
[0125] The above ingredients were placed in a stainless steel tumbler and mixed with stirring
for 1 hour. The blend obtained was injection-molded by an ordinary method at a cylinder
temperature of 200°C and a mold temperature of 40°C using an injection molding machine
(manufactured by Toyo Machinery & Metal Co., Ltd., product number: Si-50); a uniformly
colored black test piece having good appearance and surface gloss was obtained
[0126] As shown in Figure 1 (lateral view) and Figure 2 (oblique view), each test piece
10 of Examples 1 to 11 and Comparative Examples 1 to 8 and the laser absorbing test
piece 12 [all 60 mm length x 18 mm width x 3 mm thickness (1.5 mm thickness for 20
mm of the length)], were superposed with respective portions 20 mm length x 18 mm
width x 1.5 mm thickness in contact with each other.
[0127] The superposed portion was irradiated with a laser beam 14 (spot diameter 0.6 mm)
from above the test piece 10 (in the Figure) using a diode laser of 30 W output [wavelength:
940 nm, continuous] (manufactured by Fine Devices Company), while scanning at a variable
scanning speed in the lateral direction (direction perpendicular to the plane of Figure
1). Welding was conducted between test pieces of the same material.
[0128] If the test piece 10 transmits the laser ray and the laser ray is absorbed in the
laser absorbing test piece 12, the laser absorbing test piece 12 would generate heat,
by which heat the laser absorbing test piece 12 is molten around the portion that
has absorbed the laser ray, and the test piece 10 is also molten, the resins of the
two test pieces fuse together, and upon cooling the two pieces are joined together.
In Figure 2, 16 indicates the welded portion.
(6) Tensile strength test
[0129] The welded product obtained in (5) above was subjected to a tensile strength test
on both the test piece 10 side and the laser absorbing test piece 12 side in the longitudinal
direction (left-right, direction in Figure 1) at a pulling speed of 10 mm/min in accordance
with JIS K7113-1995 using a tensile strength tester (AG-50kNE, manufactured by Shimadzu
Corporation), in order to determine its tensile welding strength.
[0130] In Tables 4 and 5, Examples I to 8 describe the results for polypropylenes, Example
9 for a low-density polyethylene (LDPE), Example 10 for a high-density polyethylene
(HDPE), and Example 11 for a thermoplastic elastomer (elastomer).
Table 4
|
(1) Transmittance test (%) |
(2) Anti-sublimation test |
(3) Heat resistance test |
(4) Anti-bleeding test |
(5) Laser welding test |
(6) Tensile strength test |
Scanning speed (mm/sec) |
Surface heat (J/mm2) |
Welding state appearance |
Tensile strength (Mpa) |
GF-PP |
48 |
- |
- |
- |
|
|
|
|
Example 1 |
46 |
Good |
Good |
Good |
30 |
0.77 |
No problem |
14.8 |
45 |
0.51 |
No problem |
11.1 |
60 |
0.38 |
No problem |
3.7 |
Example 2 |
45 |
Good |
Good |
Good |
30 |
0.75 |
No problem |
14.2 |
45 |
0.50 |
No problem |
10.0 |
60 |
0.37 |
No problem |
2.5 |
Example 3 |
45 |
Good |
Good |
Good |
30 |
0.75 |
No problem |
14.5 |
45 |
0.50 |
No problem |
10.7 |
60 |
0.37 |
No problem |
3.2 |
Example 4 |
45 |
Good |
Good |
Good |
30 |
0.75 |
No problem |
14.1 |
45 |
0.50 |
No problem |
10.3 |
60 |
0.37 |
No problem |
2.9 |
Example 5 |
44 |
Good |
Good |
Good |
30 |
0.73 |
No problem |
13.5 |
45 |
0.48 |
No problem |
11.2 |
60 |
0.36 |
No problem |
3.0 |
Example 6 |
44 |
Good |
Good |
Good |
30 |
0.73 |
No problem |
14.0 |
45 |
0.48 |
No problem |
10.8 |
60 |
0.36 |
No problem |
3.7 |
Example 7 |
45 |
Good |
Good |
Good |
30 |
0.75 |
No problem |
14.8 |
45 |
0.50 |
No problem |
10.6 |
60 |
0.37 |
No problem |
3.0 |
Example 8 |
44 |
Good |
Good |
Good |
30 |
0.73 |
No problem |
14.2 |
45 |
0.48 |
No problem |
11.4 |
60 |
0.36 |
No problem |
3.6 |
Example 9 |
47 |
Good |
Good |
Good |
30 |
0.78 |
No problem |
15.7 |
45 |
0.52 |
No problem |
12.3 |
60 |
0.39 |
No problem |
5.8 |
LDPE |
58 |
- |
- |
- |
|
|
|
|
Example 10 |
53 |
Good |
Good |
Good |
30 |
0.88 |
No problem |
18.1 |
45 |
0.59 |
No problem |
17.2 |
60 |
0.44 |
No problem |
15.7 |
HOPE |
54 |
- |
- |
- |
|
|
|
|
Example 11 |
49 |
Good |
Good |
Good |
30 |
0.82 |
No problem |
19.5 |
45 |
0.54 |
No problem |
18.6 |
60 |
0.40 |
No problem |
15.1 |
Elastomer |
41 |
- |
- |
- |
|
|
|
|
Example 12 |
33 |
Good |
Good |
Good |
10 |
1.55 |
No problem |
1.1 |
15 |
1.03 |
No problem |
0.9 |
Talc PP |
30 |
- |
- |
- |
|
|
|
|
Example 13 |
26 |
Good |
Good |
Good |
10 |
130 |
No problem |
13.4 |
|
|
|
|
Table 5
|
(1) Transmittance test (%) |
(2) Anti-sublimation test |
(3) Heat resistance test |
(4) Anti-bleeding test |
(5) Laser welding test |
(6) Tensile strength test |
Scanning speed (mm/sec) |
Surface heat (J/mm2) |
Welding state appearance |
Tensile strength (Mpa) |
Comparative Example 1 |
46 |
Unacceptable |
Good |
Good |
30 |
0.77 |
No problem |
14.5 |
45 |
0.51 |
No problem |
12.3 |
60 |
0.38 |
No problem |
3.3 |
Comparative example 2 |
43 |
Unacceptable |
Good |
Good |
30 |
0.71 |
No problem |
13.2 |
45 |
0.47 |
No problem |
11.4 |
60 |
0.35 |
No problem |
1.8 |
Comparative example 3 |
46 |
Unacceptable |
Good |
Unacceptable |
30 |
0.77 |
No problem |
13.9 |
45 |
0.51 |
No problem |
11.9 |
60 |
0.38 |
No problem |
3.5 |
Comparative Example 4 |
44 |
Unaccetable |
Good |
Good |
30 |
0.73 |
No problem |
13.8 |
45 |
0.48 |
No problem |
11.6 |
60 |
0.36 |
No problem |
2.8 |
Comparative Example 5 |
47 |
Unacceptable |
Good |
Unacceptable |
30 |
0.78 |
No problem |
14.8 |
45 |
0.52 |
No problem |
12.0 |
60 |
0.39 |
No problem |
3.6 |
Comparative Example 6 |
45 |
Unacceptable |
Good |
Good |
30 |
0.75 |
No problem |
14.7 |
45 |
0.50 |
No problem |
11.4 |
60 |
0.37 |
No problem |
3.9 |
Comparative Exemple 7 |
43 |
Unacceptable |
Good |
Good |
30 |
0.71 |
No problem |
13.0 |
45 |
0.47 |
No problem |
10.1 |
60 |
0.35 |
No problem |
2.1 |
Comparative Example 8 |
43 |
Unacceptable |
Good |
Good |
30 |
0.71 |
No problem |
13.4 |
45 |
0.47 |
No problem |
10.6 |
60 |
0.35 |
No problem |
1.9 |
[0131] The colored polyolefin resin compositions of the Comparative Examples were all judged
to be unacceptable in the anti-sublimation test. The colored polyolefin resin compositions
of Comparative Examples 3 and 5 were also judged to be unacceptable in the anti-bleeding
test.
1. Laser ray transmitting colored polyolefin resin composition containing an anthraquinone
salt forming dye represented by Formula (1) below and a red azo salt forming dye:
in Formula (1),
each of A and B independently represents -NH- or -O-,
each of R1 to R3 independently represents hydrogen, an amino group, a hydroxy group or a halogen,
each of R4 to R13 independently represents hydrogen, an alkyl group, a nitro group or a sulfonic group,
Kin+ represents an organic ammonium ion,
m represents 1 or 2, and
n represents 1 or 2;
the sulfonic group is -SO3 or SO3M, the number of -SO3 being m, M representing hydrogen or an alkali metal, and each of M may be identical
or not provided that the number of SO3M is 2 or more.
2. Laser ray transmitting colored polyolefin resin composition of Claim 1, which contains
a yellow colorant, along with said anthraquinone salt forming dye and red azo salt
forming dye.
3. Laser ray transmitting colored polyolefin resin composition of Claim 1 or 2 which
contains 5 to 50% by weight of talc relative to said polyolefin resin.
4. Laser ray transmitting colored polyolefin resin composition of Claim 3, which contains
10 to 40% by weight of the talc relative to said polyolefin resin.
5. Laser ray transmitting colored polyolefin resin composition of Claim 1 or 2, wherein
said polyolefin resin is polypropylene resin.
6. Laser ray transmitting colored polyolefin resin composition of Claim 1 or 2, wherein
said polyolefin resin is a polyolefin elastomer.
7. Laser ray transmitting colored polyolefin resin composition of Claim 1 or 2, which
contains 10 to 60% by weight of reinforcing glass fiber relative to said polyolefin
resin, said polyolefin resin being polypropylene resin.
8. Method of laser welding comprising welding a portion of contact of a laser ray transmitting
material comprising a laser ray transmitting colored polyolefin resin composition
containing an anthraquinone salt forming dye represented by Formula (1) below and
a red azo salt forming dye, and a laser ray absorbing material by irradiating laser
ray so that the laser ray transmitting material transmits the laser ray and the laser
ray is absorbed in the laser ray absorbing material with the laser ray transmitting
material and the laser ray absorbing material in contact with each other:
in Formula (1),
each of A and B independently represents -NH- or -O-,
each of R1 to R3 independently represents hydrogen, an amino group, a hydroxy group or a halogen,
each of R4 to R13 independently represents hydrogen, an alkyl group, a nitro group or a sulfonic group,
Kin+ represents an organic ammonium ion,
m represents 1 or 2, and
n represents 1 or 2;
the sulfonic group is -SO3 or SO3M, the number of -SO3 being m, M representing hydrogen or an alkali metal, and each of M may be identical
or not provided that the number of SO3M is 2 or more.
9. Method of laser welding of Claim 8, wherein said laser ray transmitting colored polyolefin
resin composition contains a yellow colorant, along with said anthraquinone salt forming
dye and red azo salt forming dye.
10. Method of laser welding of Claim 8 or 9, wherein the polyolefin resin composition
contains 5 to 50% by weight of talc relative to said polyolefin resin.
11. Method of laser welding of Claim 8 or 9, wherein said polyolefin resin is polypropylene
resin and the laser ray absorbing material comprises a laser ray absorbing colored
resin composition incorporating carbon black and/or another laser absorbing colorant.
12. Method of laser welding of Claim 8 or 9, wherein a contact portion of the laser ray
transmitting material and the laser ray absorbing material is welded in a state that
satisfies Formula (A):
where
Q: amount of heat on surface of laser ray absorbing material (J/mm2)
P: output (W) of laser that laser ray transmitting material transmits
S: laser scanning speed (mm/sec)
φ : spot diameter of laser (mm).
13. Method of laser welding of Claim 8 or 9, wherein said polyolefin resin is a polyolefin
elastomer.
14. Method of laser welding of Claim 13, wherein said polyolefin elastomer is polypropylene
elastomer and the laser ray absorbing material comprises a laser ray absorbing colored
resin composition incorporating carbon black and/or another laser absorbing colorant.
15. Method of laser welding of Claim 13, wherein the laser ray absorbing material comprises
a laser ray absorbing colored resin composition incorporating carbon black and/or
another laser absorbing colorant.
16. Method of laser welding of Claim 13, wherein a contact portion of the laser ray transmitting
material and the laser ray absorbing material is welded in a state that satisfies
Formula (A):
where
Q: amount of heat on surface of laser ray absorbing material (J/mm2)
P: output (W) of laser that laser ray transmitting material transmits
S: laser scanning speed (mm/sec)
φ: spot diameter of laser (mm).
17. Method of laser welding of Claim 8 or 9, wherein said polyolefin resin composition
containing 5 to 120% by weight of reinforcing glass fiber relative to said polypropylene
resin composition.
18. Method of laser welding of Claim 17, wherein the laser ray absorbing material comprises
a laser ray absorbing colored resin composition incorporating carbon black and/or
another laser absorbing colorant.
19. Method of laser welding of Claim 17, wherein the laser ray absorbing material comprises
a laser ray absorbing colored resin composition incorporating carbon black, the primary
particle diameter of said carbon black being 15 to 50 nm.
20. Method of laser welding of Claim 17, wherein a contact portion of the laser ray transmitting
material and the laser ray absorbing material is welded in a state that satisfies
Formula (A):
where
Q: amount of heat on surface of laser ray absorbing material (J/mm2)
P: output (W) of laser that laser ray transmitting material transmits
S: laser scanning speed (mm/sec)
φ : spot diameter of laser (mm).
21. Method of laser welding of Claim 12, wherein said laser ray absorbing material comprises
a laser ray absorbing colored resin composition incorporating carbon black and/or
another laser absorbing colorant.
22. Method of laser welding of Claim 21, wherein the primary particle diameter of said
carbon black is 15 to 100 nm.
23. Method of laser welding of Claim 22, wherein the BET specific surface area of said
carbon black is 30 to 500 m2/g.
24. A use of an anthraquinone salt forming dye represented by Formula (1) below and a
red azo salt forming dye as a laser ray transmitting colorant for polyolefin resin
composition:
in Formula (1),
each of A and B independently represents -NH- or -O-,
each of R1 to R3 independently represents hydrogen, an amino group, a hydroxy group or a halogen,
each of R4 to R13 independently represents hydrogen, an alkyl group, a nitro group or a sulfonic group,
Kin+ represents an organic ammonium ion,
m represents 1 or 2, and
n represents 1 or 2;
the sulfonic group is -SO3 or SO3M, the number of -SO3 being m, M representing hydrogen or an alkali metal, and each of M may be identical
or not provided that the number of SO3M is 2 or more.
25. Use of Claim 24, wherein the polyolefin resin composition contains 5 to 50% by weight
of talc relative to said polyolefin resin.
26. Use of Claim 24. wherein said polyolefin resin being a polyolefin elastomer.
27. Use of Claim 24, wherein the polyolefin resin composition containing 10 to 60% by
weight of reinforcing glass fiber relative to said polyolefin resin, said polyolefin
resin being polypropylene resin.
28. Use of a laser ray transmitting colored polyolefin resin composition to form laser
ray transmitting colored molded material, said resin composition containing an anthraquinone
salt forming dye represented by Formula (1) below and a red azo salt forming dye.
in Formula (I),
each of A and B independently represents -NH- or -O-,
each of R1 to R3 independently represents hydrogen, an amino group, a hydroxy group or a halogen,
each of R4 to R13 independently represents hydrogen, an alkyl group, a nitro group or a sulfonic group,
Kin+ represents an organic ammonium ion,
m represents 1 or 2, and
n represents 1 or 2;
the sulfonic group is -SO3 or SO3M, the number of -SO3 being m, M representing hydrogen or an alkali metal, and each of M may be identical
or not provided that the number of SO3M is 2 or more.
29. Use of Claim 28, the laser ray transmitting colored polyolefin, resin composition
containing a yellow colorant, along with said anthraquinone salt forming dye and red
azo salt forming dye.
30. Use of claim 28 or 29 the laser ray transmitting colored polyolefin resin composition
containing 5 to 50% by weight of talc relative to said polyolefin resin.
31. Use of claim 30 the laser ray transmitting colored polyolefin resin composition containing
10 to 40% by weight of the talc relative to said polyolefin resin.
32. Use of Claim 28 or 29, wherein said polyolefin resin is polypropylene resin.
33. Use of Claim 28 or 29, wherein said polyolefin resin is a polyolefin elastomer.
34. Use of Claim 28 or 29, the laser ray transmitting colored polyolefin resin composition
containing 10 to 60% by weight of reinforcing glass fiber relative to said polyolefin
resin, said polyolefin resin being polypropylene resin.
1. Laserstrahlung durchlassende, gefärbte Polyolefinharzzusammensetzung, die einen, ein
Anthrachinonsalz bildenden Farbstoff entsprechend der nachstehenden Formel (1) und
einen, ein rotes Azosalz bildenden Farbstoff enthält:
wobei in vorstehender Formel (1):
A und B stehen je, unabhängig voneinander, für -NH- oder -O-;
R1 bis R3 stehen je, unabhängig voneinander, für Wasserstoff, für eine Aminogruppe, für eine
Hydroxygruppe oder für ein Halogen;
R4 bis R13 stehen je, unabhängig voneinander, für Wasserstoff, für eine Alkylgruppe, für eine
Nitrogruppe, oder für eine Sulfongruppe;
Kin+ steht für ein organisches Ammoniumion;
m hat einen Wert von 1 oder 2;
n hat einen Wert von 1 oder 2; und
die Sulfongruppe liegt vor in Form von -SO3 oder SO3M;
es sind m Sulfongruppen enthalten;
M steht für Wasserstoff oder für ein Alkalimetall; und
im Falle von 2 oder mehr SO3M können die M je gleich oder verschieden sein.
2. Laserstrahlung durchlassende gefärbte Polyolefinharzzusammensetzung nach Anspruch
1,
dadurch gekennzeichnet, dass
die, die Laserstrahlung durchlassende gefärbte Polyolefinharzzusammensetzung zusätzlich
zu diesem, ein Anthrachinonsalz bildenden Farbstoff und zu diesem, ein rotes Azosalz
bildenden Farbstoff ein gelbes Färbemittel enthält.
3. Laserstrahlung durchlassende gefärbte Polyolefinharzzusammensetzung nach Anspruch
1 oder 2,
dadurch gekennzeichnet, dass
die, die Laserstrahlung durchlassende gefärbte Polyolefinharzzusammensetzung
- bezogen auf das Gewicht an diesem Polyolefinharz -
zusätzlich 5 bis 50 Gew.-% Talk enthält.
4. Laserstrahlung durchlassende gefärbte Polyolefinharzzusammensetzung nach Anspruch
3,
dadurch gekennzeichnet, dass
die, die Laserstrahlung durchlassende gefärbte Polyolefinharzzusammensetzung
- bezogen auf das Gewicht an diesem Polyolefinharz -
zusätzlich 10 bis 40 Gew.-% Talk enthält.
5. Laserstrahlung durchlassende gefärbte Polyolefinharzzusammensetzung nach Anspruch
1 oder 2,
dadurch gekennzeichnet, dass
dieses Polyolefinharz ein Polypropylenharz ist.
6. Laserstrahlung durchlassende gefärbte Polyolefinharzzusammensetzung nach Anspruch
1 oder 2,
dadurch gekennzeichnet, dass
dieses Polyolefinharz ein Polyolefin-Elastomer ist.
7. Laserstrahlung durchlassende gefärbte Polyolefinharzzusammensetzung nach Anspruch
1 oder 2,
dadurch gekennzeichnet, dass
die, die Laserstrahlung durchlassende gefärbte Polyolefinharzzusammensetzung
- bezogen auf das Gewicht an diesem Polyolefinharz -
zusätzlich 10 bis 60 Gew.-% verstärkende Glasfasern enthält; und
dieses Polyolefinharz ein Polypropylenharz ist.
8. Laserschweißverfahren,
wobei ein Kontaktabschnitt aus einem Laserstrahlung durchlassenden Material,
das eine Laserstrahlung durchlassende gefärbte Polyolefinharzzusammensetzung aufweist,
die ihrerseits einen, ein Anthrachinonsalz bildenden Farbstoff entsprechend der nachstehenden
Formel (1) und einen, ein rotes Azosalz bildenden Farbstoff enthält,
mit einem Laserstrahlung absorbierenden Material verschweißt wird,
wobei mit solcher Laserstrahlung bestrahlt wird, dass dieses, die Laserstrahlung durchlassende
Material diese Laserstrahlung durchlässt, und dass die Laserstrahlung in diesem, die
Laserstrahlung absorbierenden Material, absorbiert wird,
wobei sich das, die Laserstrahlung durchlassende Material und das, die Laserstrahlung
absorbierende Material gegenseitig kontaktieren:
wobei in vorstehender Formel (1):
A und B stehen je, unabhängig voneinander, für -NH- oder -O-;
R1 bis R3 stehen je, unabhängig voneinander, für Wasserstoff, für eine Aminogruppe, für eine
Hydroxygruppe oder für ein Halogen;
R4 bis R13 stehen je, unabhängig voneinander, für Wasserstoff, für eine Alkylgruppe, für eine
Nitrogruppe, oder für eine Sulfongruppe;
Kin+ steht für ein organisches Ammoniumion;
m hat einen Wert von 1 oder 2;
n hat einen Wert von 1 oder 2; und
die Sulfongruppe liegt vor in Form von -SO3 oder SO3M
es sind m Sulfongruppen enthalten;
M steht für Wasserstoff oder für ein Alkalimetall; und
im Falle von 2 oder mehr SO3M können die M je gleich oder verschieden sein.
9. Laserschweißverfahren nach Anspruch 8,
dadurch gekennzeichnet, dass
die, die Laserstrahlung durchlassende gefärbte Polyolefinharzzusammensetzung zusätzlich
zu diesem, ein Anthrachinonsalz bildenden Farbstoff, und zu diesem, ein rotes Azosalz
bildenden Farbstoff ein gelbes Färbemittel enthält.
10. Laserschweißverfahren nach Anspruch 8 oder 9,
dadurch gekennzeichnet, dass
die, die Laserstrahlung durchlassende gefärbte Polyolefinharzzusammensetzung
- bezogen auf das Gewicht an diesem Polyolefinharz -
zusätzlich 5 bis 50 Gew.-% Talk enthält.
11. Laserschweißverfahren nach Anspruch 8 oder 9,
dadurch gekennzeichnet, dass
dieses Polyolefinharz ein Polypropylenharz ist; und
das, die Laserstrahlung absorbierende Material eine Laserstrahlung absorbierende,
gefärbte Harzzusammensetzung aufweist, die Ruß und/oder ein anderes Laserstrahlung
absorbierendes Färbemittel enthält.
12. Laserschweißverfahren nach Anspruch 8 oder 9,
dadurch gekennzeichnet, dass
ein Kontaktabschnitt, des die Laserstrahlung durchlassenden Materials mit dem, die
Laserstrahlung absorbierenden Material in einem Zustand verschweißt wird, der die
Bedingungen aus nachstehendem Ausdruck (A) erfüllt:
wobei:
Q = die Wärmemenge (J/mm2) an der Oberfläche des, die Laserstrahlung absorbierenden Materials;
P = Ausgangsleistung (W) des Lasers, dessen Strahlung durch das, die Laserstrahlung
durchlassende Material hindurchtritt;
S = Laserabtastgeschwindigkeit (mm/sec); und
φ = Spotdurchmesser (mm) des Laser.
13. Laserschweißverfahren nach Anspruch 8 oder 9,
dadurch gekennzeichnet, dass
dieses Polyolefinharz ein Polyolefin-Elastomer ist.
14. Laserschweißverfahren nach Anspruch 13,
dadurch gekennzeichnet, dass
dieses Polyolefin-Elastomer ein Polypropylen-Elastomer ist; und
das, die Laserstrahlung absorbierende Material eine Laserstrahlung absorbierende,
gefärbte Harzzusammensetzung aufweist, die Ruß und/oder ein anderes Laserstrahlung
absorbierendes Färbemittel enthält.
15. Laserschweißverfahren nach Anspruch 13,
dadurch gekennzeichnet, dass
das, die Laserstrahlung absorbierende Material eine Laserstrahlung absorbierende,
gefärbte Harzzusammensetzung aufweist, die Ruß und/oder ein anderes Laserstrahlung
absorbierendes Färbemittel enthält.
16. Laserschweißverfahren nach Anspruch 13,
dadurch gekennzeichnet, dass
ein Kontaktabschnitt, des die Laserstrahlung durchlassenden Materials mit dem, die
Laserstrahlung absorbierenden Material in einem Zustand verschweißt wird, der die
Bedingungen aus nachstehendem Ausdruck (A) erfüllt:
wobei:
Q = die Wärmemenge (J/mm2) an der Oberfläche des, die Laserstrahlung absorbierenden Materials;
P = Ausgangsleistung (W) des Lasers, dessen Strahlung durch das, die Laserstrahlung
durchlassende Material hindurchtritt;
S = Laserabtastgeschwindigkeit (mm/sec); und
φ = Spotdurchmesser (mm) des Laser.
17. Laserschweißverfahren nach Anspruch 8 oder 9,
dadurch gekennzeichnet, dass
diese Polyolefinharzzusammensetzung
- bezogen auf das Gewicht an diesem Polyolefinharz -
zusätzlich 5 bis 120 Gew.-% verstärkende Glasfasern enthält.
18. Laserschweißverfahren nach Anspruch 17,
dadurch gekennzeichnet, dass
das, die Laserstrahlung absorbierende Material eine Laserstrahlung absorbierende,
gefärbte Harzzusammensetzung aufweist, die Ruß und/oder ein anderes Laserstrahlung
absorbierendes Färbemittel enthält.
19. Laserschweißverfahren nach Anspruch 17,
dadurch gekennzeichnet, dass
das die Laserstrahlung absorbierende Material eine Laserstrahlung absorbierende, gefärbte
Harzzusammensetzung aufweist, die Ruß und/oder ein anderes Laserstrahlung absorbierendes
Färbemittel enthält; und dieser Ruß einen primären Teilchendurchmesser von 15 bis
50 nm aufweist.
20. Laserschweißverfahren nach Anspruch 17,
dadurch gekennzeichnet, dass
ein Kontaktabschnitt, des die Laserstrahlung durchlassenden Materials mit dem, die
Laserstrahlung absorbierenden Material in einem Zustand verschweißt wird, der die
Bedingungen aus nachstehendem Ausdruck (A) erfüllt:
wobei:
Q = die Wärmemenge (J/mm2) an der Oberfläche des, die Laserstrahlung absorbierenden Materials;
P = Ausgangsleistung (W) des Lasers, dessen Strahlung durch das, die Laserstrahlung
durchlassende Material hindurchtritt;
S = Laserabtastgeschwindigkeit (mm/sec); und
φ = Spotdurchmesser (mm) des Laser.
21. Laserschweißverfahren nach Anspruch 12,
dadurch gekennzeichnet, dass
dieses, Laserstrahlung absorbierende Material eine Laserstrahlung absorbierende, gefärbte
Harzzusammensetzung aufweist, die Ruß und/oder ein anderes Laserstrahlung absorbierendes
Färbemittel enthält.
22. Laserschweißverfahren nach Anspruch 21,
dadurch gekennzeichnet, dass
dieser Ruß einen primären Teilchendurchmesser von 15 bis 100 nm aufweist.
23. Laserschweißverfahren nach Anspruch 22,
dadurch gekennzeichnet, dass
dieser Ruß eine, nach dem BET-Verfahren bestimmte, spezifische Oberfläche von 30 bis
500 m2/g aufweist.
24. Verwendung
eines, ein Anthrachinonsalz bildenden Farbstoffs entsprechend der nachstehenden Formel
(1), und eines, ein rotes Azosalz bildenden Farbstoffs als ein Laserstrahlung durchlassendes
Färbemittel für eine Polyolefinharzzusammensetzung:
wobei in vorstehender Formel (1):
A und B stehen je, unabhängig voneinander, für -NH- oder -O-;
R1 bis R3 stehen je, unabhängig voneinander, für Wasserstoff, für eine Aminogruppe, für eine
Hydroxygruppe oder für ein Halogen;
R4 bis R13 stehen je, unabhängig voneinander, für Wasserstoff, für eine Alkylgruppe, für eine
Nitrogruppe, oder für eine Sulfongruppe;
Kin+ steht für ein organisches Ammoniumion;
m hat einen Wert von 1 oder 2;
n hat einen Wert von 1 oder 2; und
die Sulfongruppe liegt vor in Form von -SO3 oder SO3M;
es sind m Sulfongruppen enthalten;
M steht für Wasserstoff oder für ein Alkalimetall; und
im Falle von 2 oder mehr SO3M können die M je gleich oder verschieden sein.
25. Verwendung nach Anspruch 24,
dadurch gekennzeichnet, dass
die, die Laserstrahlung durchlassende Polyolefinharzzusammensetzung
- bezogen auf das Gewicht an diesem Polyolefinharz -
zusätzlich 5 bis 50 Gew.-% Talk enthält.
26. Verwendung nach Anspruch 24,
dadurch gekennzeichnet, dass
dieses Polyolefinharz ein Polyolefin-Elastomer ist.
27. Verwendung nach Anspruch 24,
dadurch gekennzeichnet, dass
die, die Laserstrahlung durchlassende Polyolefinharzzusammensetzung
- bezogen auf das Gewicht an diesem Polyolefinharz-
zusätzlich 10 bis 60 Gew.-% verstärkende Glasfasern enthält; und
dieses Polyolefinharz ein Polypropylenharz ist.
28. Verwendung
einer, Laserstrahlung durchlassenden gefärbten Polyolefinharz- zusammensetzung
zur Bildung eines Laserstrahlung durchlassenden gefärbten Formkörpers,
wobei diese Polyolefinharzzusammensetzung einen, ein Anthrachinonsalz bildenden Farbstoff
entsprechend der nachstehenden Formel (1) und einen, ein rotes Azosalz bildenden Farbstoff
enthält:
wobei in vorstehender Formel (1):
A und B stehen je, unabhängig voneinander, für -NH- oder-O-;
R1 bis R3 stehen je, unabhängig voneinander, für Wasserstoff, für eine Aminogruppe, für eine
Hydroxygruppe oder für ein Halogen;
R4 bis R13 stehen je, unabhängig voneinander, für Wasserstoff, für eine Alkylgruppe, für eine
Nitrogruppe, oder für eine Sulfongruppe;
Kin+ steht für ein organisches Ammoniumion;
m hat einen Wert von 1 oder 2;
n hat einen Wert von 1 oder 2; und
die Sulfongruppe liegt vor in Form von -SO3 oder SO3M;
es sind m Sulfongruppen enthalten;
M steht für Wasserstoff oder für ein Alkalimetall; und
im Falle von 2 oder mehr SO3M können die M je gleich oder verschieden sein.
29. Verwendung nach Anspruch 28,
dadurch gekennzeichnet, dass
die, die Laserstrahlung durchlassende gefärbte Polyolefinharzzusammensetzung zusätzlich
zu diesem, ein Anthrachinonsalz bildenden Farbstoff, und zu diesem, ein rotes Azosalz
bildenden Farbstoff ein gelbes Färbemittel enthält.
30. Verwendung nach Anspruch 28 oder 29,
dadurch gekennzeichnet, dass
die, die Laserstrahlung durchlassende gefärbte Polyolefinharzzusammensetzung
- bezogen auf das Gewicht an diesem Polyolefinharz -
zusätzlich 5 bis 50 Gew.-% Talk enthält.
31. Verwendung nach Anspruch 30,
dadurch gekennzeichnet, dass
die, die Laserstrahlung durchlassende gefärbte Polyolefinharzzusammensetzung
- bezogen auf das Gewicht an diesem Polyolefinharz -
zusätzlich 10 bis 40 Gew.-% Talk enthält.
32. Verwendung nach Anspruch 28 oder 29,
dadurch gekennzeichnet, dass
dieses Polyolefinharz ein Polypropylenharz ist.
33. Verwendung nach Anspruch 28 oder 29,
dadurch gekennzeichnet, dass
dieses Polyolefinharz ein Polyolefin-Elastomer ist.
34. Verwendung nach Anspruch 28 oder 29,
dadurch gekennzeichnet, dass
die, die Laserstrahlung durchlassende gefärbte Polyolefinharzzusammensetzung
- bezogen auf das Gewicht an diesem Polyolefinharz -
zusätzlich 10 bis 60 Gew.-% verstärkende Glasfasern enthält; und
dieses Polyolefinharz ein Polypropylenharz ist.
1. Composition de résine poly(oléfine) colorée transmettant un rayon laser contenant
un sel d'anthraquinone formant une teinte représentée par la formule (1) ci-dessous
et un sel azoïque rouge formant une teinte:
dans la formule (1),
chacun de A et B représente indépendamment -NH- ou -O-,
chacun de R1 à R3 représente indépendamment un atome d'hydrogène, un groupe amino, un groupe hydroxy
ou un atome d'halogène,
chacun de R4 à R13 représente indépendamment un atome d'hydrogène, un groupe alkyle, un groupe nitro
ou un groupe sulfonique,
Kin+ représente un ion ammonium organique,
m représente 1 ou 2, et
n représente 1 ou 2;
le groupe sulfonique est -SO3 ou SO3M, le nombre de -SO3 étant m, M représentant un atome d'hydrogène ou un métal alcalin, et chaque M peut
être identique ou non à condition que le nombre de SO3M soit de 2 ou plus.
2. Composition de résine poly(oléfine) colorée transmettant un rayon laser selon la revendication
1, qui contient un colorant jaune, conjointement avec ledit sel d'anthraquinone formant
une teinte et le sel azoïque rouge formant une teinte.
3. Composition de résine poly(oléfine) colorée transmettant un rayon laser selon la revendication
1 ou 2, qui contient 5 à 50 % en poids de talc par rapport à ladite résine poly(oléfine).
4. Composition de résine poly(oléfine) colorée transmettant un rayon laser selon la revendication
3, qui contient 10 à 40 % en poids du talc par rapport à ladite résine poly(oléfine).
5. Composition de résine poly(oléfine) colorée transmettant un rayon laser selon la revendication
1 ou 2, dans laquelle ladite résine poly(oléfine) est une résine poly(propylène).
6. Composition de résine poly(oléfine) colorée transmettant un rayon laser selon la revendication
1 ou 2, dans laquelle ladite résine poly(oléfine) est un élastomère poly(oléfine).
7. Composition de résine poly(oléfine) colorée transmettant un rayon laser selon la revendication
1 ou 2, qui contient 10 à 60% en poids de fibre de verre de renforcement par rapport
à ladite résine poly(oléfine), ladite résine poly(oléfine) étant une résine poly(propylène).
8. Procédé de soudage au laser comprenant le soudage d'une portion de contact d'un matériau
transmettant un rayon laser comprenant une composition de résine poly(oléfine) colorée
transmettant un rayon laser contenant un sel d'anthraquinone formant une teinte représentée
par la formule (1) ci-dessous et un sel azoïque rouge formant une teinte, et un matériau
absorbant un rayon laser en irradiant un rayon laser de sorte que le matériau transmettant
un rayon laser transmet le rayon laser et que le rayon laser est absorbé dans le matériau
absorbant un rayon laser, le matériau transmettant un rayon laser et le matériau absorbant
un rayon laser étant au contact l' un de l'autre:
dans la formule (1),
chacun de A et B représente indépendamment -NH- ou -O-,
chacun de R1 à R3 représente indépendamment un atome d'hydrogène, un groupe amino, un groupe hydroxy
ou un atome d'halogène,
chacun de R4 à R13 représente indépendamment un atome d'hydrogène, un groupe alkyle, un groupe nitro
ou un groupe sulfonique,
K1n+ représente un ion ammonium organique,
m représente 1 ou 2, et
n représente 1 ou 2;
le groupe sulfonique est -SO3 ou SO3M, le nombre de -SO3 étant m, M représentant un atome d'hydrogène ou un métal alcalin, et chaque M peut
être identique ou non à condition que le nombre de SO3M soit de 2 ou plus.
9. Procédé de soudage au laser selon la revendication 8, dans lequel ladite composition
de résine poly(oléfine) colorée transmettant un rayon laser contient un colorant jaune,
conjointement avec ledit sel d'anthraquinone formant une teinte et le sel azoïque
rouge formant une teinte.
10. Procédé de soudage au laser selon la revendication 8 ou 9, dans lequel la composition
de résine poly(oléfine) contient 5 à 50 % en poids de talc par rapport à ladite résine
poly(oléfine).
11. Procédé de soudage au laser selon la revendication 8 ou 9, dans lequel ladite résine
poly(oléfine) est une résine poly(propylène) et le matériau absorbant un rayon laser
comprend une composition de résine colorée absorbant un rayon laser incorporant du
noir de carbone et/ou un autre colorant absorbant un rayon laser.
12. Procédé de soudage au laser selon la revendication 8 ou 9, dans lequel une portion
de contact du matériau transmettant un rayon laser et du matériau absorbant un rayon
laser est soudée dans un état qui satisfait la formule (A):
où
Q: quantité de chaleur sur la surface du matériau absorbant un rayon laser (J/mm2)
P: sortie (W) d'un laser que le matériau transmettant un rayon laser transmet
S: vitesse de balayage du laser (mm/s)
φ: diamètre de point du laser (mm).
13. Procédé de soudage au laser selon la revendication 8 ou 9, dans lequel ladite résine
poly(oléfine) est un élastomère poly(oléfine).
14. Procédé de soudage au laser selon la revendication 13, dans lequel ledit élastomère
poly(oléfine) est un élastomère poly(propylène) et le matériau absorbant un rayon
laser comprend une composition de résine colorée absorbant un rayon laser incorporant
du noir de carbone et/ou un autre colorant absorbant un rayon laser.
15. Procédé de soudage au laser selon la revendication 13, dans lequel le matériau absorbant
un rayon laser comprend une composition de résine colorée absorbant un rayon laser
incorporant du noir de carbone et/ou un autre colorant absorbant un rayon laser.
16. Procédé de soudage au laser selon la revendication 13, dans lequel une portion de
contact du matériau transmettant un rayon laser et du matériau absorbant un rayon
laser est soudée dans un état qui satisfait la formule (A):
où
Q: quantité de chaleur sur la surface du matériau absorbant un rayon laser (J/mm2)
P: sortie (W) d'un laser que le matériau transmettant un rayon laser transmet
S: vitesse de balayage du laser (mm/s)
φ: diamètre de point du laser (mm).
17. Procédé de soudage au laser selon la revendication 8 ou 9, dans lequel ladite composition
de résine poly(oléfine) contient 5 à 120 % en poids de fibre de verre de renforcement
par rapport à ladite résine poly(oléfine).
18. Procédé de soudage au laser selon la revendication 17, dans lequel le matériau absorbant
un rayon laser comprend une composition de résine colorée absorbant un rayon laser
incorporant du noir de carbone et/ou un autre colorant absorbant un rayon laser.
19. Procédé de soudage au laser selon la revendication 17, dans lequel le matériau absorbant
un rayon laser comprend une composition de résine colorée absorbant un rayon laser
incorporant du noir de carbone, le diamètre de particule principal dudit noir de carbone
étant de 15 à 50 nm.
20. Procédé de soudage au laser selon la revendication 17, dans lequel une portion de
contact du matériau transmettant un rayon laser et du matériau absorbant un rayon
laser est soudée dans un état qui satisfait la formule (A):
où
Q: quantité de chaleur sur la surface du matériau absorbant un rayon laser (J/mm2)
P: sortie (W) d'un laser que le matériau transmettant un rayon laser transmet
S: vitesse de balayage du laser (mm/s)
φ: diamètre de point du laser (mm).
21. Procédé de soudage au laser selon la revendication 12, dans lequel ledit matériau
absorbant un rayon laser comprend une composition de résine colorée absorbant un rayon
laser incorporant du noir de carbone et/ou un autre colorant absorbant un rayon laser.
22. Procédé de soudage au laser selon la revendication 21, dans lequel le diamètre de
particule principal dudit noir de carbone est de 15 à 100 nm.
23. Procédé de soudage au laser selon la revendication 22, dans lequel la surface spécifique
déterminée par BET dudit noir de carbone est de 30 à 500 m2/g.
24. Utilisation d'un sel d'anthraquinone formant une teinte représentée par la formule
(1) ci-dessous et d'un sel azoïque rouge formant une teinte en tant que colorant transmettant
un rayon laser pour une composition de résine poly(oléfine):
dans la formule (1),
chacun de A et B représente indépendamment -NH- ou -O-,
chacun de R1 à R3 représente indépendamment un atome d'hydrogène, un groupe amino, un groupe hydroxy
ou un atome d'halogène,
chacun de R4 à R13 représente indépendamment un atome d'hydrogène, un groupe alkyle, un groupe nitro
ou un groupe sulfonique,
Kin+ représente un ion ammonium organique,
m représente 1 ou 2, et
n représente 1 ou 2;
le groupe sulfonique est -SO3 ou SO3M, le nombre de -SO3 étant m, M représentant un atome d'hydrogène ou un métal alcalin, et chaque M peut
être identique ou non à condition que le nombre de SO3M soit de 2 ou plus.
25. Utilisation selon la revendication 24, dans laquelle la composition de résine poly(oléfine)
contient 5 à 50 % en poids de talc par rapport à ladite résine poly(oléfine).
26. Utilisation selon la revendication 24, dans laquelle ladite résine poly(oléfine) est
un élastomère poly(oléfine).
27. Utilisation selon la revendication 24, dans laquelle la composition de résine poly(oléfine)
contient 10 à 60 % en poids de fibre de verre de renforcement par rapport à ladite
résine poly(oléfine), ladite résine poly(oléfine) étant une résine poly(propylène).
28. Utilisation d'une composition de résine poly(oléfine) colorée transmettant un rayon
laser pour former un matériau moulé coloré transmettant un rayon laser, ladite composition
de résine contenant un sel d'anthraquinone formant une teinte représentée par la formule
(1) ci-dessous et un sel azoïque rouge formant une teinte:
dans la formule (1),
chacun de A et B représente indépendamment -NH- ou -O-,
chacun de R1 à R3 représente indépendamment un atome d'hydrogène, un groupe amino, un groupe hydroxy
ou un atome d'halogène,
chacun de R4 à R13 représente indépendamment un atome d'hydrogène, un groupe alkyle, un groupe nitro
ou un groupe sulfonique,
Kin+ représente un ion ammonium organique,
m représente 1 ou 2, et
n représente 1 ou 2;
le groupe sulfonique est -SO3 ou SO3M, le nombre de -SO3 étant m, M représentant un atome d'hydrogène ou un métal alcalin, et chaque M peut
être identique ou non à condition que le nombre de SO3M soit de 2 ou plus.
29. Utilisation selon la revendication 28, la composition de résine poly(oléfine) colorée
transmettant un rayon laser contenant un colorant jaune, conjointement avec ledit
sel d'anthraquinone formant une teinte et le sel azoïque rouge formant une teinte.
30. Utilisation selon la revendication 28 ou 29, la composition de résine poly(oléfine)
colorée transmettant un rayon laser contenant 5 à 50 % en poids de talc par rapport
à ladite résine poly(oléfine).
31. Utilisation selon la revendication 30, la composition de résine poly(oléfine) colorée
transmettant un rayon laser contenant 10 à 40 % en poids du talc par rapport à ladite
résine poly(oléfine).
32. Utilisation selon la revendication 28 ou 29, dans laquelle ladite résine poly(oléfine)
est une résine poly(propylène).
33. Utilisation selon la revendication 28 ou 29, dans laquelle ladite résine poly(oléfine)
est un élastomère poly(oléfine).
34. Utilisation selon la revendication 28 ou 29, la composition de résine poly(oléfine)
colorée transmettant un rayon laser contenant 10 à 60 % en poids de fibre de verre
de renforcement par rapport à ladite résine poly(oléfine), ladite résine poly(oléfine)
étant une résine poly(propylène).